JPH09230624A - Manufacture of toner and developer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a toner to generate a high image density and establish a method for manufacturing a developer, with which excellent color tone reproducibility, easiness in the cleaning works, and stability in toner particles are ensured. SOLUTION: A base liquid for toner containing a binder resin, colorant, and organic solvent, a surface active agent, and an aqueous solution containing an inorganic dispersing agent having a mean particle size ranging between 0.1 and 2μm are mixed together, and the organic solvent and water are removed so that an intended toner is completed. Otherwise, the base liquid for toner containing a binder resin, colorant, and organic solvent, a surface active agent. and an aqueous solution containing inorganic dispersing agent are mixed together, and thereto further an inorganic dispersing agent having a mean particle size of 0.1-2μm is added, followed by removal of the organic solvent and water, and thus an intended toner is accomplished. To this toner, a carrier is added.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a toner and a method for producing a developer, which are useful for electrostatic image development.

[0002]

2. Description of the Related Art Electrophotography involves a charging step of applying a uniform electrostatic charge to a photoreceptor using a photoconductive substance, an exposure step of irradiating light to form an electrostatic latent image on the photoreceptor, A developing step of forming a toner image by attaching toner to the electrostatic latent image on the body, a transferring step of transferring the toner image to a support, and applying the toner image on the support to the support by heat, pressure, flash light, etc. This is a copying or recording technique that includes a fixing step for fixing, a cleaning step for removing toner remaining on the photoreceptor, and a charge removing step for removing an electrostatic charge on the photoreceptor and returning to an initial state. As many prints as possible can be made (US Pat. No. 2,297,691, British Patent 1,165,406 and British Patent 1,16).
5,405).

As a toner for developing an electrostatic image used in electrophotography, a toner using a polyester resin obtained by a condensation reaction of a glycol having a bisphenol skeleton and a polybasic acid (JP-A-61-7874). ), A toner using polystyrene resin (Japanese Patent Publication No. 44-16118).
JP-A-57-96354), a toner using a styrene-butyl methacrylate copolymer resin (Japanese Patent Publication No. 4-73444) and a toner using a bisphenol-type epoxy resin obtained by reacting bisphenol with epichlorohydrin. Is known.

In recent years, image formation using color toners has been required in place of conventional image formation using monochrome toners. On the other hand, in response to the trend toward higher density of information, a toner having a high resolution, that is, a toner having a small particle diameter capable of fine expression has been required. To meet such demands, a toner produced by a so-called pulverization method, in which a colorant and other additives are added to a low-molecular-weight polyester resin having excellent color tone reproducibility, and the mixture is melt-kneaded and then pulverized. Has been used. However, this toner has the following problems. (1) The dispersion of the colorant and other additives during melt-kneading is insufficient, and the color tone of the fixed image is not sufficient. Further, the composition of the toner becomes heterogeneous, and the image quality is not sufficient. (2) Finely pulverized particles are likely to be generated during stirring by a developing machine,
The image quality at the time of printing may be degraded, and toner may be scattered to contaminate the surrounding environment.

[0005]

The invention according to claim 1 provides a method for producing a toner which is excellent in color tone reproducibility, cleaning property and stability of toner particles and has a high image density. In addition to the effect of the invention described in claim 1, the invention described in claim 2 provides a method for producing a toner having further excellent stability of toner particles. The third aspect of the present invention provides a method for producing a toner having excellent color tone reproducibility, cleaning property, toner particle stability, and high image density. In addition to the effect of the invention described in claim 2 or 3, the invention described in claim 4 provides a method for producing a toner in which fogging and toner scattering are suppressed. The invention according to claim 5 provides a method for producing a developer which is excellent in color tone reproducibility, cleaning property and stability of toner particles and has a high image density.

[0006]

Means for Solving the Problems The present invention includes the following (1) to
(5). (1) After mixing a toner mother liquor containing a binder resin, a colorant and an organic solvent, an aqueous solution containing a surfactant and an inorganic dispersant having an average particle diameter of 0.1 to 2 μm, the organic solvent and water are removed. A method for producing a toner, comprising: (2) After mixing a toner mother liquor containing a binder resin, a colorant and an organic solvent and an aqueous solution containing a surfactant and an inorganic dispersant having an average particle size of 0.1 to 2 μm, the average particle size is further reduced to 0. The method for producing a toner according to (1) above, wherein an inorganic dispersant having a thickness of 1 to 2 μm is added. (3) After mixing a toner mother liquor containing a binder resin, a colorant and an organic solvent and an aqueous solution containing a surfactant and an inorganic dispersant, further adding an inorganic dispersant to remove the organic solvent and water. And a method for producing a toner. (4) The toner according to (2) or (3) above, wherein the total amount of the inorganic dispersant contained in the aqueous solution and the amount of the inorganic dispersant added is 1 to 16% by weight based on the toner mother liquor. Manufacturing method. (5) A method for producing a developer, which comprises adding a carrier to the toner produced by the method according to any one of (1) to (4).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the binder resin used in the present invention include a polyester resin and a vinyl polymer obtained by polymerizing a polymerizable vinyl monomer. The polyester resin can be produced by a known synthesis method using an alcohol component and an acid component as raw materials.

As the alcohol component, for example, a compound represented by the general formula (I)

Embedded image (Wherein, R ¹ and R ² are ethylene groups or propylene groups, x and y are each an integer of 1 or more, and the sum of x and y is 4 to 14). Propylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3,3)-
2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2,0) -polyoxyethylene (2, 0) -2,2-
Bis (4-hydroxyphenyl) propane, etc.], ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, isopentyl glycol, hydrogenated bisphenol A, 1,3-butanediol,
1,4-butanediol, neopentyl glycol, xylylene glycol, 1,4-cyclohexanedimethanol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, bis- (β-hydroxyethyl) terephthalate, tris- (β -Hydroxyethyl) isocyanurate, 2,2,4-trimethylolpentane-1,3-diol and the like.

Of these alcohol components, trihydric or higher alcohols are preferable from the viewpoint of stability such as fixing strength and offset resistance, but the blending amount is 40 mol% or less of the total alcohol components. The above alcohol components are used alone or in combination of two or more.

Examples of the acid component include malonic acid, succinic acid, glutaric acid, dimer acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, isophthalic acid dimethyl ester, terephthalic acid dimethyl ester, terephthalic acid monomethyl ester and tetrahydro. Phthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, dimethyltetrahydrophthalic acid, endomethylenehexahydrophthalic acid, naphthalenetetracarbic acid, diphenolic acid, trimellitic acid, pyromellitic acid, trimesic acid, cyclopentanedicarboxylic acid , 3,3 ', 4,4'
-Benzophenonetetracarboxylic acid, 1,2,3,4-
Butanetetracarboxylic acid, 2,2-bis- (4-carboxyphenyl) propane, anhydrides of these acids (maleic anhydride, trimellitic anhydride, etc.), trimellitic anhydride and 4,4-diaminophenylmethane Isocyanate ring obtained from trimerized reaction product of diimide carboxylic acid, tris- (β-carboxyethyl) isocyanurate, polyimide carboxylic acid containing isocyanurate ring, tolylene diisocyanate, xylylene diisocyanate or isophorone diisocyanate, and trimellitic anhydride Containing polyimide carboxylic acid.

Among these acid components, a carboxylic acid having a valency of 3 or more is preferable from the viewpoints of stability such as fixing strength and offset resistance, but the content thereof is 40 mol% or less based on the total acid components. The above acid components are used alone or in combination of two or more.

In addition to the alcohol component and the acid component, a hydroxycarboxylic acid component (p-oxybenzoic acid, vanillic acid, dimethylolpropionic acid, malic acid, tartaric acid,
-Hydroxyisophthalic acid, etc.) can also be added,
When the hydroxycarboxylic acid component is added, its amount is 0.7 to 17 mol% of the total monomer components. The polyester resin is composed of the alcohol component and the acid component (in some cases,
Further, the above-mentioned hydroxycarboxylic acid component) can be produced by a condensation reaction according to a conventional method. For example, the alcohol component and the acid component are blended in a reaction vessel,
150 to 190 ° C in the presence of an inert gas (such as nitrogen gas)
At a temperature of 200 to 250 ° C. for 6 to 8 hours.
It can be manufactured by heating for a time and obtaining a reactant. The alcohol component and the acid component can be blended in a range conventionally used, but usually they are blended at a ratio of the hydroxyl group / carboxyl group in a molar ratio of 1/2 to 2/1. The acid value of the obtained polyester resin is not particularly limited, but is usually 1 to 20.

In producing the polyester resin, a catalyst may be added. When the carboxylic acid component used is a free carboxylic acid containing no ester group, examples of the catalyst include esterification catalysts (dibutyltin dilaurate, dibutyltin oxide and other organic metals, and tetrabutyl titanate and other metal alkoxides). ) Can be used, and the amount thereof is preferably 0.1 to 1% by weight based on the total amount of the raw materials. When the carboxylic acid component is a lower alkyl ester, examples of the catalyst include transesterification catalysts (metal acetates such as zinc acetate, lead acetate and magnesium acetate, metal oxides such as zinc oxide and antimony oxide, and tetraoxides). Metal alkoxides such as butyl titanate) can be used, and the compounding amount thereof is 0.005 to the total amount of the raw materials.
It is preferably 0.05% by weight.

The glass transition temperature of the polyester resin is 3
The temperature is preferably 5 to 100 ° C, and more preferably 50 to 90 ° C from the viewpoint of the balance between storage stability and toner fixability. If the glass transition temperature is lower than 35 ° C., the toner tends to cause blocking (a phenomenon in which toner particles aggregate and agglomerate) during storage or in a developing machine. On the other hand, when the glass transition temperature exceeds 100 ° C,
A large amount of heat energy tends to be required for fixing the toner. The said polyester resin is used individually or in combination of 2 or more types.

The polymerizable vinyl-based monomer used to obtain the vinyl-based polymer is, for example, styrene, a styrene derivative (α-methylstyrene, vinyltoluene, p
-T-butylstyrene, etc.), alkyl acrylate (methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate,
Pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, etc.), alkyl methacrylate (methyl methacrylate, ethyl methacrylate, propyl methacrylate) , Butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate,
Dodecyl methacrylate). The polymerizable vinyl monomers are used alone or in combination of two or more.

Further, the above polymerizable vinyl-based monomer may be used in combination with other vinyl-based monomers (described later) other than these. The amount of the polymerizable vinyl-based monomer used is preferably 50% by weight or more, and more preferably 70% by weight or more, based on all the monomers.

Other vinyl monomers include, for example, 1
Vinyl monomers having one vinyl group in the molecule, for example, acrylic acid, methacrylic acid, acrylic acid derivatives other than alkyl acrylate (glycidyl acrylate, methoxyethyl acrylate, propoxyethyl acrylate, acrylic acid Butoxyethyl, methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxyethylene glycol acrylate, butoxytriethylene glycol acrylate, methoxydipropylene glycol acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxytetraethylene glycol acrylate, Benzyl acrylate, cyclohexyl acrylate,
Tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, N-vinyl-2-pyrrolidone acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, 2-hydroxy acrylate -3-Phenyloxypropyl, glycidyl acrylate, acrylonitrile, acrylamide, N-methylol acrylamide, diacetone acrylamide, etc.), methacrylic acid derivatives other than methacrylic acid alkyl esters (glycidyl methacrylate, methoxyethyl methacrylate, propoxyethyl methacrylate), Butoxyethyl methacrylate, methoxydiethylene glycol methacrylate, ethoxydiethylene glycol methacrylate, methoxymethacrylate Ethylene glycol, butoxytriethylene glycol methacrylate, methoxydipropylene glycol methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxytetraethylene glycol methacrylate, benzyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, methacrylic acid Dicyclopentenyl, dicyclopentenyloxyethyl methacrylate, N-vinyl-2-pyrrolidone methacrylate, methacrylonitrile, methacrylamide, N-methylolmethacrylamide, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxy methacrylate Butyl, methacrylic acid 2-hydroxy-
3-phenyloxypropyl, vinyl pyridine, etc. are mentioned. The other vinyl-based monomers are used alone or in combination of two or more.

Further, a monomer having two or more vinyl groups in one molecule may be used in combination, which is used as a crosslinking agent. As the monomer having two or more vinyl groups in one molecule, a monomer having two vinyl groups in one molecule is preferable from the viewpoint of stability such as fixing strength and offset resistance. Examples of such a monomer include divinylbenzene, a reaction product of glycol with methacrylic acid or acrylic acid (ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3- Butylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,
5-pentanediol diacrylate, 1,5-pentanediol dimethacrylate, etc.). The amount of these monomers used is preferably 20% by weight or less based on all the monomers.

As the vinyl polymer, styrene is 50% by weight based on all monomers in view of balance of various properties.
A polymer obtained by using any of the above alkyl acrylates and alkyl methacrylates or a mixture thereof in a total amount of 50% by weight or more based on the remaining monomers is preferable.

The method for polymerizing the vinyl monomer is as follows:
For example, known polymerization methods such as suspension polymerization, solution polymerization, emulsion polymerization and bulk polymerization can be used. In the solution polymerization, for example, an organic solvent such as xylene is put into a reaction device equipped with a cooling pipe, a stirrer, a nitrogen gas introduction pipe and a thermometer, and a solution containing a vinyl-based monomer and a polymerization initiator is added dropwise thereto. ,
A vinyl polymer can be obtained by heating to polymerize the monomer and then removing the solvent. In suspension polymerization, for example, a reaction device equipped with a cooling pipe, a stirrer, a nitrogen gas introduction pipe and a thermometer is used, and a mixture of a vinyl monomer and a polymerization initiator is added to a solvent containing a dispersant. Then, the dispersion state is obtained, and the monomer is polymerized by heating.
The heating temperature is 10 to 10 hours lower than the 10-hour half-life temperature of the polymerization initiator.
Preferably, the temperature is higher by 20 ° C. The polymerization initiator may be partially added during heating. After the polymer is formed, the vinyl polymer can be obtained by performing ordinary dehydration and drying.

Weight average molecular weight (Mw) of vinyl polymer
Is preferably 2,500 to 150,000, and more preferably 3,000 to 45,000. If the weight average molecular weight is less than 2,500, the toner tends to be crushed at the time of printing, resulting in 150,000.
If it exceeds, the fixability tends to decrease, and the color tone reproducibility tends to deteriorate. The weight average molecular weight is a value measured by gel permeation chromatography and expressed in terms of standard polystyrene.

The glass transition temperature of the vinyl polymer is preferably from 35 to 100 ° C., preferably from 50 to 90 ° C.
C. is more preferable. Glass transition temperature is 35 ℃
When the amount is less than the range, the toner tends to cause blocking (a phenomenon in which toner particles aggregate and agglomerate) during storage or in a developing machine. On the other hand, when the glass transition temperature exceeds 100 ° C., a large amount of heat energy tends to be required for fixing the toner. The above vinyl polymers are used alone or in combination of two or more.

As the binder resin, from the viewpoint that coloring of the resin itself is suppressed and coloring with a colorant is efficiently performed, a resin composed of only a polyester resin or a resin composed of only a vinyl polymer is preferable. A mixture obtained by adding another resin to a vinyl polymer may be used. As other resins, for example, amide resin, urethane resin, urea resin, epoxy resin, silicone resin, xylene resin,
Diene resin, styrene resin (however, compound not included in the above-mentioned vinyl polymer), acrylic resin (however, compound not included in the above-mentioned vinyl polymer), styrene-acryl resin (however, the above-mentioned vinyl Compounds not included in the polymer), phenolic resins, terpene resins, coumarin resins, amide imide resins, butyral resins, urethane resins, ethylene / vinyl acetate resins, and the like.

The amide resin is prepared, for example, by polymerizing caprolactam, dibasic acids (terephthalic acid, isophthalic acid, adipic acid, maleic acid, succinic acid, sebacic acid, thioglycolic acid, etc.) and diamines (ethylenediamine, diamino acid). Ethyl ether, 1,4-diaminobenzene, 1,4-diaminobutane, etc.). The urethane resin is obtained, for example, by subjecting diisocyanates (p-phenylene diisocyanate, p-xylene diisocyanate, 1,4-tetramethylene diisocyanate, etc.) and glycols (ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, etc.) to an addition reaction. be able to.

Urea resins include, for example, diisocyanates (p-phenylene diisocyanate, p-xylene diisocyanate, 1,4-tetramethylene diisocyanate, etc.) and diamines (ethylenediamine, diaminoethyl ether, 1,4-diaminobenzene, 1,4 4-diaminobutane) according to a conventional method. Epoxy resins include, for example, amines (ethylamine, butylamine, etc.), acrylic acid or methacrylic acid derivatives (acrylonitrile, methacrylonitrile, acrylamide, etc.), vinyl ethers (vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, etc.). , Vinyl ketones (vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, etc.),
It can be obtained from N-vinyl compounds (N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone and the like), vinylnaphthalene and the like according to a conventional method.

The compounding amount of the above-mentioned other resin is preferably 50% by weight or less with respect to the total amount of the binder resin. On the other hand, the compounding amount of the other resin is preferably 30% by weight or less based on all components (hereinafter referred to as toner components) added to the organic solvent to obtain a toner mother liquor.

The amount of the binder resin is determined from the viewpoint of the balance between the binding strength of the toner image to the support and the hiding power of the toner image.
It is preferably 60 to 95% by weight, more preferably 80 to 95% by weight, based on the toner component, and 8
More preferably, it is 5 to 90% by weight. If the blending amount is less than 60% by weight, the binding force of the toner image to the support becomes weak, and when the support of the toner image is bent or rubbed, the toner image is lost and information is easily lost. Tends to become. On the other hand, if it exceeds 95% by weight, the hiding power of the toner image tends to be insufficient and the print quality tends to be poor.

The colorant is variously selected depending on whether the toner to be obtained is a black toner or a color toner, and various organic pigments, inorganic pigments and dyes can be used. Examples of the colorant used for obtaining the black toner include carbon black, acetylene black, iron black, aniline black, cyanine black, and the like, among which carbon black is preferable. Examples of the colorant used for obtaining the color toner include a yellow colorant, a red colorant, a blue colorant, an orange colorant, a purple colorant, and a green colorant.

As the yellow colorant, for example, naphthol yellow S (CI10316), Hansa yellow 10G (C.
I.11710), Hansa Yellow 5G (CI1166)
0), Hansa Yellow G (CI11680), Hansa Yellow R (CI12710), Pigment Yellow L (CI1
2720), benzidine yellow G (CI21095),
Permanent Yellow NCG (CI20040), Vulcan First Yellow 5G (CI21220), Quinoline Yellow (CI47005), Permanent Yellow FGL
(CI11767), permanent yellow HR (CI2
1108) and the like.

Examples of the red colorant include permanent red 4R (CI12070) and para red (CI1
2120), Brilliant Fast Scarlet (CI
12315), Brilliant Carmin BS (CI123
51), permanent red F4R (CI1233)
5), Balkan Fast Rubin B (CI1232
0), Light Fast Red Toner B (CI124
50), Lake Red C (CI15585: 1), Brilliant Carmine 6B (CI15850: 1), Rhodamine Lake B (CI45170: 2) and the like.

Examples of the blue colorant include cobalt blue (CI77346) and alkali blue lake (CI
42750: 1), Victoria Blue Lake (CI44
045: 2), metal-free phthalocyanine blue (CI74
100), phthalocyanine blue (CI74160),
Fast Sky Blue (CI74180: 1) and the like. Examples of the orange colorant include permanent orange (CI12075), Vulcan fast orange GG (CI21165), and indanthrene brilliant orange RG (CI59300). Examples of purple colorants include First Violet B
(CI12321), methyl violet lake (CI
42535) and the like. Examples of green colorants include Pigment Green B (CI10006), Acid Green Lake, and Phthalocyanine Green (CI7
4260).

The above colorants are used alone or in combination of two or more. From the viewpoint of the balance between the hiding power and the fixing power of the toner, the amount of the colorant blended is preferably 0.1 to 15% by weight with respect to the toner component.
The amount is more preferably 10% by weight, further preferably 3 to 5% by weight. If the content of the colorant is less than 0.1% by weight, the hiding power tends to be insufficient and poor printing quality tends to be obtained, and if it exceeds 15% by weight, the fixing power tends to decrease.

The organic solvent is not particularly limited as long as it can dissolve the binder resin, and examples thereof include hydrocarbons (toluene, xylene, hexane etc.), halogenated hydrocarbons (methylene chloride, chloroform, dichloroethane). , Dichloroethylene, etc.), alcohol or ether (ethanol, butanol, benzyl alcohol ethyl ether, benzyl alcohol isopropyl ether, tetrahydrofuran, tetrahydropyran, etc.),
Ester (methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate, etc.), ketone or acetal (acetone,
Methyl ethyl ketone, diisobutyl ketone, dimethyl oxide, diacetone alcohol, cyclohexanone, methylcyclohexanone, etc.) and the like. The amount of the organic solvent used is not particularly limited as long as the toner mother liquor can be granulated in an aqueous solution, but from the viewpoint of toner granulation easiness and toner yield, it is 50% relative to the toner mother liquor. ~ 9
It is preferably 0% by weight, more preferably 60 to 80% by weight, and further preferably 70 to 75% by weight.

Various additives can be added to the organic solvent in addition to the binder resin and the colorant according to the intended use of the toner to be obtained. Examples of the additive include a magnetic or magnetizable material, an anti-offset agent, a positively or negatively charged charge control agent, and silica powder. A magnetic or magnetizable material is added to obtain a toner for developing an electrostatic image having magnetism, and examples of such a material include oxides of iron, cobalt, nickel and the like (hematite, magnetite, etc.). . The magnetic or magnetizable material is used alone or in combination of two or more.

The blending amount of the magnetic or magnetizable material is appropriately selected depending on whether the toner to be obtained is a magnetic toner or a non-magnetic toner. In the case of a non-magnetic toner, toner scattering is suppressed. In view of this, the content is preferably 0.5 to 5% by weight, more preferably 1 to 4% by weight, and further preferably 2 to 3% by weight based on the toner component. If the blending amount is less than 0.5% by weight, the effect of suppressing toner scattering tends to be hardly obtained, and if it exceeds 5% by weight, the fixing property tends to decrease.

Examples of the anti-offset agent include lower alcohol esters of fatty acids (such as butyl stearate and propyl stearate), higher alcohol esters of fatty acids (such as casta wax and diamond wax), and higher alcohol esters (such as palm acetyl and Hoechst wax E). , Hoechst wax OP, carnauba wax, etc.), alkylene bis fatty acid amide compounds (bisamide blast flow, amide 6L, 7S, 6H, Hoechst wax C, etc.), olefin monomers (ethylene, propylene, butene, hexene, heptene, etc.) Octene, nonene, decene, 3-methyl-1-butene, 3-methyl-2
-Pentene, 3-propyl-5-methyl-2-hexene, etc.) or a copolymer of these olefin monomers with acrylic acid, methacrylic acid, butyl acetate, etc. Among these offset preventing agents, polypropylene is preferable from the viewpoint that it can meet various conditions of electrophotography. The above offset preventing agents are used alone or in combination of two or more kinds.

From the viewpoint of the balance between the effect of preventing the offset and the powder fluidity of the toner, the compounding amount of the above-mentioned offset preventing agent is preferably 0.1 to 10% by weight based on the toner component, More preferably, the content is 5% by weight. If the blending amount is less than 0.1% by weight, a sufficient offset preventing effect tends to be difficult to be exhibited, and if it exceeds 10% by weight, the powder fluidity of the toner is lowered and the developability is deteriorated. There is a tendency that the transparency of the toner is lowered and it is difficult to obtain a desired color tone.

As the positively chargeable charge control agent, for example,
Nigrosine dyes of azine compounds (Bontron 03 (trade name of Orient Chemical Industry Co., Ltd.), etc.), quaternary ammonium salts (Bontron P-51 (trade name of Orient Chemical Industry Co., Ltd.), etc.), quaternary ammonium salts Molybdenum complex (T
P-302 (trade name of Hodogaya Chemical Co., Ltd.), TP-41
5 (trade name of Hodogaya Chemical Co., Ltd.), quaternary ammonium salt (Copy Charge PSY VP)
2038 (trade name of Hoechst), triphenylmethane derivative (Copy Blue P)
R (trade name of Hoechst), LRA-901
(Nippon Carlit Co., Ltd. product name) and the like.
Among these positively chargeable charge control agents, the quaternary ammonium salt molybdenum complex is preferable from the viewpoint of excellent charge stability.

Examples of the negatively charged charge control agent include, for example,
Metal-containing azo dye (Bontron S-34 (trade name of Orient Chemical Industry Co., Ltd.), etc.), oxynaphthoic acid metal complex (E-82 (trade name of Orient Chemical Industry Co., Ltd.), etc.), salicylic acid metal complex ( E-84 (Orient Chemical Industry
(Trade name, etc.), phenol-based condensate (E-89 (trade name, Orient Chemical Industry Co., Ltd.), etc.), quaternary ammonium salt (Copy Charge NEG VP2)
036, Copy Charge NX VP434 (both are trade names of Hoechst, etc.), boron complex (LR-147)
(Nippon Carlit Co., Ltd. product name) and the like.
Among these negatively chargeable charge control agents, the boron complex is preferable from the viewpoint of excellent charge stability. These positively or negatively chargeable charge control agents are used alone or in combination of two or more. When two or more types are combined, a combination of positively chargeable charge control agents, a negatively chargeable charge control agent Any combination of the combination of the positive charge control agent and the negative charge control agent may be used.

These charge control agents are used within a range that does not hinder the color tone of the toner image to be fixed. The amount of the charge control agent is 0.5 to 5.0% by weight based on the toner components. Is preferably 0.5 to 3% by weight, more preferably 1 to 3% by weight. If the blending amount is less than 0.5% by weight, the charging effect tends to be difficult to obtain, while the blending amount is 5% by weight.
When the value exceeds the above, the charge amount becomes high from the beginning, and therefore the print density is low, the transferability from the photoconductor to the toner support is poor, and the cleaning property of the transfer residual toner adhering to the photoconductor is poor. Problems tend to occur.

Known silica powders can be used. Examples of such silica powder include Aerosil R972, R974, Silica D-17, T-805, R-812, and RA.
200, HRX-C (both are trade names of Nippon Aerosil Co., Ltd.), Talanox 500 (trade name of Tarco), Cab
-O-Sil M-5, MS-7, MS-75, HS-
5, EH-5, S-17, TS-72 (all are trade names of Cabot Co.). Among these silica powders, RA200 is preferable because of its excellent fluidity and charge stability. The silica powder is used alone or in combination of two or more kinds. When these silica powders are blended, the blending amount is preferably 0.5 to 3% by weight with respect to the toner component,
More preferably, it is 5 to 1% by weight. If the blending amount is less than 0.5% by weight, the effect of improving the fluidity tends to be hardly obtained, and if it exceeds 3% by weight,
The fixability of the toner tends to decrease.

A toner mother liquor is prepared by adding the above-mentioned binder resin, colorant, and additives (if necessary) to an organic solvent. At this time, using a high-viscosity agitator Haydon Suriwan Motor 600G (trade name, manufactured by Shinto Scientific Co., Ltd.),
It is preferable to stir under a stirring condition in which the peripheral speed of rotation of the rotor is 0.75 to 1.7 m / sec. The viscosity of the toner mother liquor is measured by an E-type viscometer at a shear rate of 76.8 m / s at 25 ° C. from the viewpoint of dispersion of the toner mother liquor in the aqueous solution.
1 to 30 mPa · s is preferable, and 20 to 30 mPa · s is preferable.
Is more preferable. This viscosity is 1mPa ・ s10cp
If it is less than 30 mPa · s or more than 30 mPa · s, the dispersion becomes insufficient, and the yield of the toner having a particle diameter of 3 to 20 μm tends to decrease.

The toner mother liquor is mixed with an aqueous solution containing a surfactant and an inorganic dispersant, and known surfactants can be used, for example, anionic type, cationic type and nonionic type interfaces. Activators may be mentioned. Examples of the anionic surfactant include sodium alkylbenzenesulfonate, sodium α-olefin sulfonate, sodium alkylsulfonate, and sodium alkyldiphenyletherdisulfonate. Examples of the cation-type surfactant include alkylamine salts (stearylamine hydrochloride, dioleylamine sulfate, etc.), quaternary alkylammonium salts (stearyltrimethylammonium chloride, etc.), amine oxides (lauryldimethylamine oxide, etc.). And so on. Examples of nonionic surfactants include polyoxyethylene alkyl ethers (polyoxyethylene lauryl ether etc.),
Examples thereof include polyoxyethylene alkylaryl ether (polyoxyethylene nonylphenyl ether and the like), sorbitan fatty acid ester (sorbitan monolaurate and the like) and the like.

Among these surfactants, anionic ones are preferred from the viewpoint of excellent stability of oil droplets.
From the viewpoints of toner stability and resolution when used in combination with an inorganic dispersant, sodium alkylbenzene sulfonate is particularly preferable. These surfactants are used alone or in combination of two or more. The blending amount of these surfactants is 1 × 10 ^{−5 to} 0.1 with respect to the toner mother liquor from the viewpoint of the balance between the particle size distribution of the toner and the cleaning power.
% By weight. This amount is 1 × 10 ^-5
If the amount is less than 0.1% by weight, the particle size distribution of the toner tends to be wide, and if it exceeds 0.1% by weight, the detergency tends to decrease. After adding the toner mother liquor, these surfactants may be further added to the aqueous solution. The toner may be added during the dispersion of the toner particles or after the end of the dispersion.

Examples of the inorganic dispersant include tricalcium phosphate, hydroxyapatite, calcium carbonate, titanium oxide, silica powder and the like. Among these inorganic dispersants, tricalcium phosphate and hydroxyapatite are preferable in terms of granulation properties, stability thereof, and extremely little adverse effect on the properties of the obtained toner. The average particle size of the inorganic dispersant is preferably from 0.1 to 2 μm. When the average particle diameter is less than 0.1 μm, the particle diameter of the obtained toner tends to be too small,
When the ratio exceeds, the particle diameter of the obtained toner tends to be too large.

The average particle diameter referred to here is the photon correlation method by laser scattering, the submicron particle analyzer-colter (SUB-MICRON PARTI).
CLE ANALYZER, Model N4MD, COULTER ELECTRO
(Made by NICS) is used to disperse SDPIN in a 10 ppm sodium dodecylbenzenesulfonate solution.
It is the average particle diameter measured in the TENSITY RESULTS mode. Dispersion into a 10 ppm sodium dodecylbenzenesulfonate solution was carried out by using an ultrasonic disperser having a frequency of 40 kHz for 1 minute.

The inorganic dispersant is previously dispersed in an aqueous solution to which the toner mother liquor is added, but the stability of the toner particles is excellent, whereby the color tone reproducibility and the cleaning property are excellent, and the toner scattering can be suppressed. From this point of view, it is preferable to add these inorganic dispersants to the above aqueous solution after adding the toner mother liquor. The toner may be added during the dispersion of the toner particles or after the end of the dispersion. Here, “after dispersion” includes the time of removing the organic solvent and water described later. The blending amount of the inorganic dispersant is appropriately determined according to the particle size when the toner mother liquor is granulated in the aqueous solution, but from the viewpoint of the balance between the granulation of toner particles and the yield, the total amount of the blending amount is It is preferably 1 to 16% by weight based on the toner mother liquor. If the total amount of this compounding amount is 1% by weight, granulation is difficult to be performed sufficiently and aggregates tend to be formed, and if it exceeds 16% by weight, unnecessary fine particles are generated, and the objective It tends to be difficult to obtain particles in high yield.

When the inorganic dispersant is dispersed in the aqueous solution in advance, the compounding amount of the inorganic dispersant is 0.5 to 8% by weight based on the toner mother liquor from the viewpoint of narrowing the range of particle size distribution. And preferably 3 to 6% by weight. If the content is less than 0.5% by weight, the particle size of the dispersed particles tends to increase, and if it exceeds 8% by weight, the particle size distribution tends to widen. The amount of the inorganic dispersant added after the addition of the toner mother liquor is preferably 0.5 to 8% by weight with respect to the toner mother liquor from the viewpoint of narrowing the range of particle size distribution. Is more preferable. If the content is less than 0.5% by weight, aggregates tend to be formed, and if it exceeds 8% by weight, target particles tend to be difficult to obtain in high yield. From the viewpoint of narrowing the particle size distribution, the inorganic dispersant is added to the toner mother liquor in an amount of 0.
It is preferable to disperse 5 to 8% by weight, and to add 0.5 to 8% by weight to the toner mother liquor during or after the dispersion of the toner particles (that is, after the granulation of the toner particles). .

The toner mother liquor is mixed with an aqueous solution containing a surfactant and an inorganic dispersant. At this time, it is preferable to stir under high speed shear using an apparatus equipped with a high speed shear mechanism. Various types of high-speed dispersers can be used as devices provided with the high-speed shearing mechanism, and examples of the high-speed dispersers include homogenizers. Here, the homogenizer means that substances that are incompatible with each other pass through a narrow gap between the casing (fixing plate) and the rotor that rotates at high speed, whereby a substance that is incompatible with the liquid is converted into fine particles in a certain liquid. Refers to a device for dispersing in In the present invention,
The substances incompatible with each other correspond to an aqueous solution containing an inorganic dispersant and a surfactant and a toner mother liquor. Examples of such a homogenizer include, for example, TK homomixer, line flow homomixer (both trade names of Tokushu Kika Kogyo Co., Ltd.), Silverson homogenizer (trade name of Silverson Company), Polytron homogenizer (Kinematica (KI)).
NEMATICA) AG company product name) and the like. When stirring using a homogenizer, the peripheral speed of the rotor blades is preferably 8 m / sec or more. This peripheral speed is 8m /
If it is less than a second, micronization tends to be insufficient.

By the above stirring operation, oil droplets of the toner mother liquor are granulated in the aqueous solution, and the volume average particle diameter thereof is 4-1.
It is preferably 0 μm. This volume average particle diameter is 4
If it is less than μm, the fluidity tends to deteriorate and the image quality tends to deteriorate, and if it exceeds 10 μm, the melting and mixing properties are insufficient when the three primary colors are mixed to develop an intermediate color during the production of a full-color toner. Therefore, it is difficult to produce an intermediate color, and it is difficult to increase the resolution. Furthermore, from the viewpoint of charge stability of the obtained toner and fluidity of the toner particles,
The amount of the fine particles having a particle size of 3 μm or less is set to 7% by volume or less based on the total amount of the obtained toner particles, and the amount of the coarse particles having a particle size exceeding 20 μm is minimized (preferably to 0% by volume). Is preferred. In addition, these particle diameters are measured using a Coulter Counter TA-II (trade name of Nikkaki Co., Ltd.).

After granulating the toner particles, the organic solvent and water are removed to obtain a toner. The operation of removing the organic solvent may be, for example, vaporizing the organic solvent at room temperature and atmospheric pressure, but in order to shorten the time required to remove the organic solvent, the temperature is lower than the boiling point of the organic solvent used, and 80 ° C difference from boiling point
It is set within the following range, and the degree of vacuum is 146 × 10 ² to 4
It is preferable to vaporize at 80 × 10 ² Pa.

After removing the organic solvent, the pH of the aqueous solution is from 1 to 1 from the viewpoint of improving the characteristics by making the composition of the toner original.
It is preferable to add an acid (hydrochloric acid, sulfuric acid, formic acid, acetic acid, etc.) to the aqueous solution so as to obtain 3, and stir the aqueous solution to remove the inorganic dispersant remaining on the surfaces of the toner particles. To remove water from an aqueous solution containing toner, for example,
The aqueous solution may be dehydrated using a centrifuge and dried at 40 to 50 ° C. using a vacuum dryer. The residual water content of the toner is preferably 0.3% by weight or less based on the total amount of the obtained toner.

The obtained toner can be used for electrostatic image development. In order to further improve physical properties such as fluidity and chargeability, the toner contains fine particles (fine silica powder, vinyl-based polymer or copolymer, zinc stearate, aluminum oxide, etc.) as external additives. , Titanium oxide, etc.) may be added to and mixed with the toner so that these fine particles are attached to the surface of the toner particles. The amount of these external additives added is 0.05 to 5% by weight in total with respect to the toner, from the viewpoint of the balance between charge stability and fluidity of the toner.
And preferably 0.2 to 0.5% by weight.

The obtained toner can be mixed with a carrier to form a developer. The type of carrier is not particularly limited, and known materials such as iron oxide powder, various ferrites, and magnetite can be used. The mixing ratio of the toner and the carrier is not particularly limited, and a known mixing ratio can be used. Usually, the toner is used in an amount of 1 to 10% by weight based on the developer. Each step of electrophotography when using the toner and developer obtained by the production method of the present invention, that is,
As the charging step, the exposure step, the transfer step, the fixing step, the cleaning step, and the charge removal step, any of the known steps can be used.

[0055]

The present invention will be described in detail below with reference to examples. In addition, in Tables 1-4 and Tables 6-9, the unit of the blending amount of the raw materials is parts by weight. Examples 1 to 8 and Comparative Example 1 (1) Production of Polyester Resin An acid component and an alcohol component shown in Table 1 were charged into a reaction vessel, and the temperature was gradually increased while blowing nitrogen gas.
The condensation reaction was allowed to proceed at 0 ° C. for 5 hours, and then the reaction was completed at 230 ° C. The glass transition temperature of the obtained resin is also shown in Table 1.

[0056]

[Table 1]

(2) Production of toner Using a ball mill, the binder resin, colorant (pigment), organic solvent and additives shown in Table 2 are stirred until the pigment particles become submicron, to produce a toner mother liquor. did.

[0058]

[Table 2]

Using a homogenizer, the obtained toner mother liquor is added to an aqueous solution containing an inorganic dispersant and a surfactant under the conditions shown in Table 3 and the peripheral speed of the rotor is 11 to 19.
The mixture was stirred at m / sec at a temperature of 35 ° C., and an inorganic dispersant and a surfactant were added after the dispersion was completed. The particle size at this time is shown in Table 3. In Table 3, the hydroxyapatite 5% by weight aqueous solution is trisodium phosphate 12
An aqueous solution in which 166 parts by weight of calcium chloride was added dropwise to an aqueous solution in which 391 parts by weight of a hydrate and 13 parts by weight of sodium hydroxide were added, and the mixture was stirred at 20 to 30 ° C. to obtain a stirring speed and The reaction temperature was adjusted so that the average particle size of hydroxyapatite was 0.02μ.
m, 0.1 μm, 0.6 μm, 0.8 μm, 1.0 μ
A 5% by weight aqueous solution of various hydroxyapatite having m, 1.2 μm and 6 μm was obtained.

[0060]

[Table 3]

After the dispersion was completed, the organic solvent was distilled off under normal pressure or reduced pressure under the temperature condition which was lower than the boiling point of the solvent and the difference from the boiling point was 80 ° C. or less. When toluene is used as the solvent, the temperature is 60 to 75 ° C., and the degree of vacuum is 237 × 10 ^{2 to} 3
84 × 10 ² Pa, and when methylene chloride is used,
When methyl ethyl ketone is used at a temperature of 20 to 30 ° C. and normal pressure, the temperature is 50 to 70 ° C. and the degree of vacuum is 237 × 10
^{2 to} 384 × 10 ² Pa. After removing the organic solvent, the aqueous solution containing the toner was cooled, 35% concentrated hydrochloric acid was added to the aqueous solution until the pH reached 2, and the mixture was stirred to wash the toner with water, whereby the inorganic dispersant was washed away. The remaining aqueous solution was dried and classified to obtain a solid toner having a volume average particle size in the range of 4 to 8 μm. The amount of residual toluene in the toner obtained when toluene was used as the organic solvent was 0.1% by mass based on the toner as a result of measurement by a gas chromatography method. Further, with respect to 100 parts by weight of the obtained toner, Table 4 is further added.
The toner external additive shown in (4) was added, and the mixture was stirred and mixed with a Henschel mixer to obtain a toner containing the external additive.

[0062]

[Table 4]

(3) Evaluation 95% by weight of a copper-zinc ferrite carrier having an average particle diameter of 40 μm and coated with an acrylic resin-modified silicone resin.
Was added with 5% by weight of a toner to obtain a developer. A full color printer QMSColor Script La that can print 8 sheets of A4 size paper per minute using this developer.
25 using the ser1000 (trade name of QMS company)
Continuous printing was performed in an environment of ℃ and 60% relative humidity. The obtained printed matter was evaluated according to the following criteria.

(A) Reproducibility of color tone: It was printed on OHP (overhead projector) paper, and the reproducibility of a color image was examined by OHP and evaluated according to the following criteria. Very good: A chromatic color is developed, and an intermediate color is also developed. Good: Intermediate between "extremely good" and "poor". Inferior: chromatic color does not appear. (B) Image density, fog and resolution Image density and fog were measured using a Macbeth reflection densitometer RD514 (A division kollmorgen Corp. trade name). For the resolution, the image of the Electrophotographic Society of Japan Chart No. 5-2 was copied, and the image was magnified 10 times to find how many lines of equal width and even intervals (line pair / mm) per 1 mm were resolved. It was visually determined whether or not there is any.

(C) Toner scattering The presence or absence of toner scattering was visually determined. (D) Cleanability The transfer residual toner on the photoreceptor that has passed through the cleaning process is transferred to a blank sheet using Scotch tape (trade name of Sumitomo 3M Limited).
It was measured with a Macbeth reflection densitometer RD514, and the difference from the blank was examined. Those having a difference of 0.04 or less were evaluated as "very good", those having cleaning properties equivalent thereto were evaluated as "good", and those not corresponding thereto were evaluated as "poor".

Example 9 As the toner, the toners obtained in Examples 1, 2 and 3 in Table 2 were used and blended with the carrier in the above proportion to obtain a developer. Using these toners and developers, a Konica Digital Full Color 9028 type copier (manufactured by Konica) was used to adjust the initial image, and then printing was performed. The intermediate colors were also accurately reproduced, and the image quality was good. .

Comparative Example 2 The binder resin, colorant and additive of Example 1 in Table 2 were premixed with a Henschel mixer and then melt-kneaded with a biaxial kneader. Next, this kneaded product was cooled and pulverized by a pin mill and a jet mill to obtain an irregular toner having an average particle diameter of 8 μm. In addition, Aerosil R972
(Nippon Aerosil Co., Ltd. product name) is 0.
2% by weight was added, mixed with a Henschel mixer, and evaluated in the same manner as in Example 9. The evaluation was performed both at the initial stage and after printing 10,000 pages. Table 5 shows the results. The toner yield is 80 to 90% by weight for the toner yields of Examples 1 to 8.
However, it was as low as 60% by weight.

Comparative Example 3 Except that the aqueous solution containing the inorganic dispersant of Example 1 in Table 3 was changed to an aqueous solution containing 3% by weight of polyvinyl alcohol (Denka Poval W-24 (trade name of Denki Kagaku Kogyo KK)). Is the same as in Example 1, and the average particle size is 6 μm.
m spherical toner was obtained. The performance of the obtained toner was evaluated in the same manner as in Example 9. The evaluation was performed both at the initial stage and after printing 2,000 pages. Table 5 shows the results. The toner yield was as low as 20% by weight. This toner was not environmentally stable.

[0069]

[Table 5]

Examples 10 to 17 and Comparative Example 4 (1) Production of Binder Resin 300 g of xylene as a solvent was charged in a pressure reaction vessel,
The temperature was raised to 130 ° C., and 100 g of the polymerizable vinyl monomer shown in Table 6 and a polymerization initiator were added dropwise to the xylene over 3 hours. After the reaction was allowed to proceed for 6 hours to complete the reaction, about 90% by weight of xylene was removed by distillation under reduced pressure and was taken out of the reaction vessel. Then, the solvent removal was continued for 12 hours at a temperature of 180 ° C. under a reduced pressure of 133.3 Pa or less with a vacuum dryer,
A vinyl polymer was obtained. Table 6 also shows the glass transition temperature and molecular weight (weight average molecular weight (Mw), number average molecular weight (Mn), degree of molecular weight dispersion (Mw / Mn)) of the obtained resin. The weight average molecular weight and the number average molecular weight in Table 6 are values measured by gel permeation chromatography and expressed in terms of standard polystyrene.

[0071]

[Table 6]

(2) Manufacture of Toner The procedure of “(2) Manufacture of toner” in “Examples 1 to 8 and Comparative Example 1” was followed. However, the composition of the binder resin, the colorant (pigment), the organic solvent and the additive are shown in Table 7, and the dispersion conditions are shown in Table 8.
The composition of the external additive was as shown in Table 9. The hydroxyapatite used had an average particle diameter of 0.1 μm.

[0073]

[Table 7]

[0074]

[Table 8]

[0075]

[Table 9]

(3) Evaluation In accordance with "(3) Evaluation" of "Examples 1 to 8 and Comparative Example 1", the results are shown in Table 10. However, as a copier,
Recopy FT7 that can print 65 sheets of 4 size paper per minute
570 (trade name of Ricoh Co., Ltd.) was used for continuous printing in an environment of 35 ° C. and 70% relative humidity.

Example 18 Example 18 was carried out except that the toners obtained in Examples 10 to 12 in Table 8 were used as the toner. As a result, the printed matter
The intermediate colors were also accurately reproduced, and the image quality was good.

Comparative Example 5 Comparative Example 2 was followed except that the binder resin, pigment and charge control agent of Example 10 in Table 7 were used. However, the evaluation was performed both at the initial stage and after printing 50,000 pages. Table 10 shows the results.
The yield of the toner was as low as 60% by weight, whereas the yield of the toners of Examples 10 to 17 was 80% by weight or more.

Comparative Example 6 Comparative Example 3 was followed except that the inorganic dispersant shown in Example 10 of Table 8 was used. However, the evaluation was performed both at the initial stage and after printing 5,000 pages. Table 10 shows the results.
The yield of the toner was as low as 20% by weight. This toner was not environmentally stable.

[0080]

[Table 10]

As shown in Table 5, when the toners obtained in Examples 7 and 8 were used, the color tone reproducibility, resolution and cleaning property were good even after printing 30,000 pages, and the image density was high. , Toner scattering was small, and fogging was also small. Further, when the toners obtained in Examples 1 to 6 were used, 3
Even after printing many pages, the color tone reproducibility, resolution, and cleanability were extremely excellent, the image density was extremely high, there was no toner scattering, and there was almost no fogging. On the other hand, when the toner obtained in Comparative Example 2 was used, the color tone reproducibility was poor, the resolution was low, the toner was scattered, and the fog was large even after printing 10,000 pages. Further, when the toner obtained in Comparative Example 3 was used, the color tone reproducibility was poor, the resolution was low, the toner was scattered, and the cleaning property was poor even after printing 2,000 pages. Further, as shown in Table 3, in Comparative Example 1, oil droplet coalescence occurred, and toner particles could not be formed.

On the other hand, as shown in Table 10, Example 1
When the toners obtained in Nos. 6 and 17 were used, color tone reproducibility, resolution and cleanability were good, image density was high, toner scattering was small, and fog was small even after printing 50,000 pages. Further, when the toners obtained in Examples 10 to 15 were used, the color tone reproducibility, resolution, and cleanability were extremely excellent even after printing 50,000 pages, the image density was extremely high, toner was not scattered, and almost no fogging was observed. Did not. On the other hand, when the toner obtained in Comparative Example 5 was used, color tone reproducibility was poor when printing 50,000 pages, the resolution was low, and toner scattering was large. Further, when the toner obtained in Comparative Example 6 was used, the color tone reproducibility was poor, the resolution was low, the toner was scattered, and the cleaning property was poor even after printing 5,000 pages. Also,
As shown in Table 8, in Comparative Example 4, defective oil droplets occurred,
The toner particles could not be granulated.

[0083]

The method for producing a toner according to claim 1 is suitable for producing a toner having a high image density, which is excellent in color tone reproducibility, cleaning property, and stability of toner particles. The method for producing a toner according to claim 2 exhibits the effect of the invention according to claim 1, and is suitable for producing a toner having further excellent stability of toner particles. The method for producing a toner according to claim 3,
It has excellent cleaning properties and toner particle stability, and is suitable for producing a toner having a high image density. The method for producing a toner according to claim 4 has the effects of the invention according to claim 2 or 3, and is suitable for producing a toner in which fogging and toner scattering are suppressed. The method for producing a developer according to claim 5 is excellent in color tone reproducibility, cleanability, and stability of toner particles, and is suitable for producing a developer having a high image density.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Yugo Kumagai, 4-13-1, Higashi-machi, Hitachi, Ibaraki Prefecture, Yamazaki Plant, Hitachi Chemical Co., Ltd. (72) Chiaki Okada, 4-13, Higashi-machi, Hitachi, Ibaraki No. 1 inside the Yamazaki Plant of Hitachi Chemical Co., Ltd.

Claims (5)

[Claims] 1. A toner mother liquor containing a binder resin, a colorant and an organic solvent, a surfactant and an average particle size of 0.1 to 2.
A method for producing a toner, which comprises mixing an aqueous solution containing an inorganic dispersant having a diameter of μm, and then removing the organic solvent and water. 2. A toner mother liquor containing a binder resin, a colorant and an organic solvent, a surfactant and an average particle size of 0.1 to 2.
The method for producing a toner according to claim 1, further comprising adding an inorganic dispersant having an average particle diameter of 0.1 to 2 μm after mixing an aqueous solution containing the inorganic dispersant having a diameter of μm. 3. A toner mother liquor containing a binder resin, a colorant and an organic solvent, and an aqueous solution containing a surfactant and an inorganic dispersant are mixed, and then an inorganic dispersant is further added to remove the organic solvent and water. A method for producing a toner, comprising: 4. The total amount of the inorganic dispersant contained in the aqueous solution and the inorganic dispersant added is 1 with respect to the toner mother liquor.
The method for producing a toner according to claim 2 or 3, wherein the amount is -16% by weight. 5. A method for producing a developer, which comprises adding a carrier to the toner produced by the method according to any one of claims 1 to 4.